PRODUCTION OF LARGE-PORE SILICON DIOXIDES AND THEIR APPLICATION IN CHROMIUM CATALYSTS FOR OLEFIN POLYMERIZATION

Claims

1. A silicon dioxide-based composite characterized by bulk density in the range from 0.08 to 0.4 g / ml; total pore volume from 0.4 to 2.5 ml / g; specific surface area according to the BET method from 175 to 375 m 2 / g; and maximum pore diameter from 10 to 80 nm, where 0.5 to 40% of the total pore volume of the silica-based composite is accounted for by pores with diameters in the range of 30 to 100 nm.

2. A silicon dioxide-based composite according to claim 1, characterized in that the average pore diameter of said silicon dioxide-based composite is from 10 to 50 nm.

3. A silicon dioxide-based composite according to claim 1, characterized in that bulk density ranges from 0.1 to 0.35 g / ml; the total pore volume ranges from 0.5 to 2 ml / g; The specific surface area according to the BET method ranges from 200 to 375 m 2 / g; and the maximum pore diameter ranges from 15 to 50 nm.

4. A silicon dioxide-based composite according to claim 1, characterized in that from 40 to 85% of the total pore volume of the silica-based composite is accounted for by pores with diameters in the range from 10 to 50 nm; from 1 to 25% of the total pore volume of the silica-based composite is accounted for by pores with diameters less than or equal to 5 nm; and less than or 4% of the total pore volume of the silica-based composite is accounted for by pores with diameters less than or equal to 3 nm.

5. A silicon dioxide-based composite according to claim 1, characterized in that from 1 to 35% of the total pore volume of the silicon dioxide-based composite are pores with diameters in the range from 30 to 100 nm.

6. A silicon dioxide-based composite according to claim 1, characterized in that from 2 to 35% of the total pore volume of the silicon dioxide-based composite are pores with diameters in the range from 30 to 100 nm.

7. A silicon dioxide-based composite according to claim 1, characterized in that the average pore diameter of said silicon dioxide-based composite is from 9 to 30 nm.

8. A silicon dioxide-based composite according to claim 1, characterized in that 40 to 85% of the total pore volume of the silicon dioxide-based composite is accounted for by pores with diameters in the range of 10 to 50 nm.

9. A silicon dioxide-based composite according to claim 1, characterized in that from 1 to 25% of the total pore volume of the said silica-based composite is accounted for by pores with diameters less than or equal to 5 nm; and less than or 4% of the total pore volume of the said silica-based composite is accounted for by pores with diameters less than or equal to 3 nm.

10. A silicon dioxide-based composite according to claim 1, characterized in that the average pore diameter of the said silicon dioxide-based composite is from 10 to 50 nm; from 1 to 25% of the total pore volume of the said silica-based composite is accounted for by pores with diameters less than or equal to 5 nm; and less than or 4% of the total pore volume of the said silica-based composite is accounted for by pores with diameters less than or equal to 3 nm.

11. A silicon dioxide-based composite according to paragraph 3, characterized in that from 40 to 85% of the total pore volume of the silica-based composite is accounted for by pores with diameters in the range from 10 to 50 nm; from 1 to 25% of the total pore volume of the silica-based composite is accounted for by pores with diameters less than or equal to 5 nm; and less than or 4% of the total pore volume of the silica-based composite is accounted for by pores with diameters less than or equal to 3 nm.

12. A silicon dioxide-based composite according to claim 3, characterized in that the average pore diameter of said silicon dioxide-based composite is from 10 to 50 nm.

13. A silicon dioxide-based composite according to claim 12, characterized in that from 1 to 35% of the total pore volume of the silicon dioxide-based composite are pores with diameters in the range from 30 to 100 nm.

14. A silicon dioxide-based composite according to claim 3, characterized in that 40 to 85% of the total pore volume of the silicon dioxide-based composite is accounted for by pores with diameters in the range of 10 to 50 nm.

15. A silicon dioxide-based composite according to claim 3, characterized in that from 1 to 25% of the total pore volume of the said silica-based composite is accounted for by pores with diameters less than or equal to 5 nm; and less than or 4% of the total pore volume of the said silica-based composite is accounted for by pores with diameters less than or equal to 3 nm.

16. A silicon dioxide-based composite according to paragraph 3, characterized in that the average pore diameter of the said silicon dioxide-based composite is from 10 to 50 nm; from 1 to 25% of the total pore volume of the said silica-based composite is accounted for by pores with diameters less than or equal to 5 nm; and less than or 4% of the total pore volume of the said silica-based composite is accounted for by pores with diameters less than or equal to 3 nm.

17. A silicon dioxide-based composite according to claim 3, characterized in that from 2 to 35% of the total pore volume of the silicon dioxide-based composite are pores with diameters in the range from 30 to 100 nm.

18. A silicon dioxide-based composite according to claim 3, characterized in that the average pore diameter of said silicon dioxide-based composite is from 9 to 30 nm.

19. A silicon dioxide-based composite characterized by: bulk density in the range from 0.08 to 0.4 g / ml; total pore volume from 0.4 to 2.5 ml / g; specific surface area according to the BET method from 175 to 375 m2 / g; and maximum pore diameter from 10 to 80 nm, where 40 to 85% of the total pore volume of the silica composite is accounted for by pores with diameters in the range of 10 to 50 nm.

20. A silicon dioxide-based composite according to claim 19, characterized in that the average pore diameter of said silicon dioxide-based composite is from 10 to 50 nm.

21. A silicon dioxide-based composite according to claim 19, characterized in that the average pore diameter of said silicon dioxide-based composite is from 9 to 30 nm.

22. A silicon dioxide-based composite according to claim 19, characterized in that from 2 to 35% of the total pore volume of the silicon dioxide-based composite are pores with diameters in the range from 30 to 100 nm.

23. A silicon dioxide-based composite according to claim 19, characterized in that bulk density ranges from 0.1 to 0.35 g / ml; the total pore volume ranges from 0.5 to 2 ml / g; The specific surface area according to the BET method ranges from 200 to 375 m 2 / g; and the maximum pore diameter ranges from 15 to 50 nm.

24. A silicon dioxide-based composite according to claim 23, characterized in that less than 20% of the total pore volume of the silicon dioxide-based composite is accounted for by pores with diameters less than or equal to 5 nm.

25. A silicon dioxide-based composite according to claim 19, characterized in that bulk density ranges from 0.12 to 0.34 g / ml; the total pore volume ranges from 0.4 to 1.5 ml / g; The specific surface area according to the BET method ranges from 190 to 375 m 2 / g; and The maximum pore diameter ranges from 17 to 40 nm.

26. A silicon dioxide-based composite according to claim 25, characterized in that less than 4% of the total pore volume of the silicon dioxide-based composite is accounted for by pores with diameters less than or equal to 3 nm.

27. A silicon dioxide-based composite characterized by bulk density in the range from 0.08 to 0.4 g / ml; total pore volume from 0.4 to 2.5 ml / g; specific surface area according to the BET method from 175 to 375 m2 / g; and maximum pore diameter from 10 to 80 nm, where 1 to 25% of the total pore volume of the silica composite is accounted for by pores with diameters less than or equal to 5 nm; and less than or 4% of the total pore volume of the silica-based composite is accounted for by pores with diameters less than or equal to 3 nm.

28. A silicon dioxide-based composite according to claim 27, characterized in that the average pore diameter of said silicon dioxide-based composite is from 9 to 30 nm.

29. A silicon dioxide-based composite according to claim 27, characterized in that bulk density ranges from 0.1 to 0.35 g / ml; the total pore volume ranges from 0.5 to 2 ml / g; The specific surface area according to the BET method ranges from 200 to 375 m 2 / g; and the maximum pore diameter ranges from 15 to 50 nm.

30. A method for producing a composite based on silicon dioxide, comprising (1) combining the silicon dioxide component I and the silicon dioxide component II in a diluent containing at least 70% by weight of water to form a mixture; and (2) forming a silicon dioxide-based composite in said mixture; wherein: Component I silicon dioxide contains silicon dioxide particles of irregular and non-spherical shape, characterized by an average aspect ratio of at least 2:1 and a specific surface area according to the BET method in the range from 150 to 1000 m 2 / G; component II of silicon dioxide comprises colloidal silicon dioxide; and The silicon dioxide based composite is characterized by: bulk density from 0.08 to 0.4 g / ml; total pore volume from 0.4 to 2.5 ml / g; specific surface area according to the BET method from 175 to 375 m 2 / g; and maximum pore diameter from 10 to 80 nm.

31. The method according to claim 30, wherein the silicon dioxide component I comprises highly dispersed silicon dioxide.

32. The method according to paragraph 30, further comprising: combining a chromium-containing compound and an optional titanium-containing compound with a silica-based composite to form a supported chromium catalyst; and calcination of chromium catalyst on a substrate.

33. The method according to claim 30, in which step (1) comprises combining the chromium-containing compound and the optional titanium-containing compound with the silicon dioxide component I and the silicon dioxide component II in a diluent to form a mixture; and step (2) involves obtaining a chromium catalyst on a support in the said mixture.

34. The method according to claim 30, wherein the colloidal silicon dioxide is characterized by an average particle size d50 of 3 to 25 nm.

35. The method according to claim 30, wherein the amount of component II silicon dioxide based on the total amount of component I silicon dioxide and component II silicon dioxide is in the range from 2 to 25 wt.%.

36. The method according to claim 30, wherein the silicon dioxide component I is non-porous.

37. The method of claim 30, wherein the average aspect ratio is from 3:1 to 50:

1.

38. The method of claim 30, wherein step (1) comprises combining the titanium-containing compound with the silicon dioxide component I and the silicon dioxide component II in a diluent.

39. The method of claim 30, wherein the supported chromium catalyst contains from 0.5 to 5 wt.% chromium based on the total weight of the catalyst.

40. The method according to claim 30, wherein the chromium catalyst on the support contains from 0.5 to 5 wt.% chromium based on the total weight of the catalyst.

41. A method for producing a composite based on silicon dioxide, comprising: (1) combining the silicon dioxide component I and the silicon dioxide component II in a solvent to form a mixture; and (2) forming a silicon dioxide-based composite in said mixture; wherein: Component I of silicon dioxide includes highly dispersed silicon dioxide; component II of silicon dioxide comprises a silicon compound; and The silicon dioxide based composite is characterized by: bulk density in the range from 0.08 to 0.4 g / ml; total pore volume from 0.4 to 2.5 ml / g; specific surface area according to the BET method from 175 to 375 m 2 / g; and maximum pore diameter from 10 to 80 nm.

42. The method of claim 41, wherein the silicon compound comprises a silicon alkoxide, a silicon halide, a silicon hydride, a silane, a hydrocarbyl silane, a siloxane, or any combination thereof.

43. The method of claim 41, wherein the silicon compound comprises sodium silicate, ethyl silicate, a silicate oligomer, or any combination thereof.

44. The method according to paragraph 41, further comprising combining a chromium-containing compound and an optional titanium-containing compound with a silica-based composite to form a supported chromium catalyst; and calcination of chromium catalyst on a substrate.

45. The method according to paragraph 41, in which step (1) comprises combining the chromium-containing compound and the optional titanium-containing compound with the silicon dioxide component I and the silicon dioxide component II in a solvent to form a mixture; and step (2) involves obtaining a chromium catalyst on a support in the said mixture.

46. ​​The method according to claim 41, wherein the amount of component II silicon dioxide based on the total amount of component I silicon dioxide and component II silicon dioxide is in the range from 10 to 90 wt.%.

47. The method according to claim 41, wherein the silicon dioxide component I is non-porous.

48. The method of claim 41, wherein step (1) comprises combining the titanium-containing compound with the silicon dioxide component I and the silicon dioxide component II in a solvent.

49. The method of claim 44, wherein the supported chromium catalyst contains from 0.5 to 5 wt.% chromium based on the total weight of the catalyst.

50. The method of claim 45, wherein the supported chromium catalyst contains from 0.5 to 5 wt.% chromium based on the total weight of the catalyst.